Direct Vinylation of Alcohols or Aldehydes Employing Alkynes as Vinyl Donors: A Ruthenium Catalyzed C−C Bond-Forming Transfer Hydrogenation

Patman, Ryan L.; Chaulagain, Mani Raj; Williams, Vanessa M.; Krische, Michael J.

doi:10.1021/ja809456u

Cited by 128 publications

(56 citation statements)

References 57 publications

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“…Remarkably, a fourth mechanism for the coupling of primary alcohols with alkynes is evident in couplings that form allylic alcohols 59 or conjugated enones (Scheme 9). 60 These processes are catalyzed by (TFA) 2 Ru(CO)(PPh 3 ) 2 in the absence of added phosphine ligand.…”

Section: Conversion Of Primary Alcohols To Secondary Alcoholsmentioning

confidence: 99%

Ruthenium-Catalyzed Transfer Hydrogenation for C–C Bond Formation: Hydrohydroxyalkylation and Hydroaminoalkylation via Reactant Redox Pairs

et al. 2016

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Section: Conversion Of Primary Alcohols To Secondary Alcoholsmentioning

confidence: 99%

Ruthenium-Catalyzed Transfer Hydrogenation for C–C Bond Formation: Hydrohydroxyalkylation and Hydroaminoalkylation via Reactant Redox Pairs

et al. 2016

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“…Carbonyl addition through a closed six-centered transition state accounts for the observed anti -diastereoselectivity (Scheme 18). Interestingly, under the conditions of ruthenium-catalyzed transfer hydrogenation, alkynes couple to alcohols or aldehydes to provide products of carbonyl vinylation [278]. Here, isomerization of the vinyl-ruthenium intermediate to the σ-allylruthenium intermediate is not observed.…”

Section: Iridium-catalyzed Transfer Hydrogenation For C–c Bond Formmentioning

confidence: 99%

Formation of C–C Bonds via Iridium-Catalyzed Hydrogenation and Transfer Hydrogenation

2010

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The formation of C-C bonds via catalytic hydrogenation and transfer hydrogenation enables carbonyl and imine addition in the absence of stoichiometric organometallic reagents. In this review, iridium-catalyzed C-C bond-forming hydrogenations and transfer hydrogenations are surveyed. These processes encompass selective, atom-economic methods for the vinylation and allylation of carbonyl compounds and imines. Notably, under transfer hydrogenation conditions, alcohol dehydrogenation drives reductive generation of organoiridium nucleophiles, enabling carbonyl addition from the aldehyde or alcohol oxidation level. In the latter case, hydrogen exchange between alcohols and π-unsaturated reactants generates electrophile-nucleophile pairs en route to products of hydro-hydroxyalkylation, representing a direct method for the functionalization of carbinol C-H bonds.

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“…For example, racemic allylic alcohols 45 and ( Z )-homoallylic alcohols 46 are formed through mechanisms that involve alkyne-carbonyl oxidative coupling (not shown). Oxidative coupling is suppressed by exogenous iodide and careful selection of phosphine ligand, allowing hydrometalative pathways to dominate.…”

Section: Catalytic Enantioselective Alcohol C-h Functionalizationmentioning

confidence: 99%

Catalytic Enantioselective Carbonyl Allylation and Propargylation via Alcohol-Mediated Hydrogen Transfer: Merging the Chemistry of Grignard and Sabatier

2017

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Conspectus Merging the characteristics of transfer hydrogenation and carbonyl addition, we have developed a new class of catalytic enantioselective C-C bond formations. In these processes, hydrogen transfer between alcohols and π-unsaturated reactants generates carbonyl-organometal pairs that combine to deliver products of addition. Based on this mechanistic paradigm, lower alcohols are converted directly to higher alcohols in the absence of premetalated reagents or discrete alcohol-to-carbonyl redox reactions. In certain cases, due to a pronounced kinetic preference for primary vs secondary alcohol dehydrogenation, diols and higher polyols are found to engage in catalytic stereo- and site-selective C-C bond formation - a capability that further enhances efficiency by enabling skeletal construction events without extraneous manipulations devoted to the installation and removal of protecting groups. While this Account focuses on redox-neutral couplings of alcohols, corresponding aldehyde reductive couplings mediated by 2-propanol were developed in parallel for most catalytic transformations reported herein. Mechanistically, two distinct classes of alcohol C-H functionalizations have emerged, which are distinguished by the mode of pronucleophile activation; specifically, processes wherein alcohol oxidation is balanced by (a) π-bond hydrometalation or (b) C-X bond reductive cleavage. Each pathway offers access to allylmetal or allenylmetal intermediates and, therefrom, enantiomerically enriched homoallylic or homopropargylic alcohol products, respectively. In the broadest terms, carbonyl addition mediated by premetalated reagents has played a central role in synthetic organic chemistry for well over a century, however, the requisite organometallic reagents pose issues of safety, require multistep syntheses and generate stoichiometric quantities of metallic byproducts. The concepts and catalytic processes described in this Account, conceived and developed wholly within the author’s laboratory, signal a departure from the use of stoichiometric organometallic reagents in carbonyl addition. Rather, they reimagine carbonyl addition as a hydrogen auto-transfer process or cross-coupling in which alcohol reactants, by virtue of their native reducing ability, drive generation of transient organometallic nucleophiles and, in doing so, serve dually as carbonyl proelectrophiles. The catalytic allylative and propargylative transformations developed thus far display capabilities far beyond their classical counterparts and their application to the total synthesis of type I polyketide natural products have evoked a step-change in efficiency. More importantly, the present data suggest that diverse transformations traditionally reliant on premetalated reagents may now be conducted catalytically without stoichiometric metals. This Account provides the reader and potential practitioner with a catalog of enantioselective alcohol-mediated carbonyl additions – a user’s guide, 10-year retrospective, and foundation for future work in this ...

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Direct Vinylation of Alcohols or Aldehydes Employing Alkynes as Vinyl Donors: A Ruthenium Catalyzed C−C Bond-Forming Transfer Hydrogenation

Cited by 128 publications

References 57 publications

Ruthenium-Catalyzed Transfer Hydrogenation for C–C Bond Formation: Hydrohydroxyalkylation and Hydroaminoalkylation via Reactant Redox Pairs

Ruthenium-Catalyzed Transfer Hydrogenation for C–C Bond Formation: Hydrohydroxyalkylation and Hydroaminoalkylation via Reactant Redox Pairs

Formation of C–C Bonds via Iridium-Catalyzed Hydrogenation and Transfer Hydrogenation

Catalytic Enantioselective Carbonyl Allylation and Propargylation via Alcohol-Mediated Hydrogen Transfer: Merging the Chemistry of Grignard and Sabatier

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